CN107915711B - Method for synthesizing ethylene carbonate - Google Patents
Method for synthesizing ethylene carbonate Download PDFInfo
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- CN107915711B CN107915711B CN201610878316.XA CN201610878316A CN107915711B CN 107915711 B CN107915711 B CN 107915711B CN 201610878316 A CN201610878316 A CN 201610878316A CN 107915711 B CN107915711 B CN 107915711B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
Abstract
The invention relates to a method for synthesizing ethylene carbonate, which mainly solves the problem of low activity of a heterogeneous catalyst in the prior art. The invention is characterized in that the method comprises a step of contacting ethylene oxide and carbon dioxide with a catalyst under reaction conditions; the catalyst comprises: at least one component AA selected from the amino acids lysine, arginine, histidine, alanine, glycine, glutamic acid, tryptophan or aspartic acid; and at least one component HPA selected from phosphotungstic acid, silicotungstic acid, germanotungstic acid, arsenotungstic acid, phosphomolybdic acid, silicomolybdic acid, germanomolybdic acid or arsenomolybdic acid; the technical scheme that the weight ratio of AA to HPA is 1/40-1/4 better solves the problem, and can be used in industrial production of preparing ethylene carbonate from ethylene oxide and carbon dioxide.
Description
Technical Field
The invention relates to a method for synthesizing vinyl carbonate, in particular to a method for synthesizing vinyl carbonate by using ethylene oxide and carbon dioxide.
Background
The ethylene carbonate is a solvent with excellent performance and a fine chemical intermediate, and is a potential basic raw material for organic chemical industry. At the same time, CO2Is a greenhouse gas, and how to effectively fix the greenhouse gas becomes one of the most challenging issues in the century. By the addition of ethylene oxide and CO2The reaction synthesis of ethylene carbonate is a good fixing method. With the recent increasing interest in the CO-production of dimethyl carbonate and ethylene glycol starting from ethylene carbonate, CO is fixed by cyclic carbonates2The approach of (a) has also received increasing attention.
Heterogeneous catalysts for the production of cyclic carbonates have been reported to include MgO, MgO/Al2O3And Cs/KX, etc., all of which have a problem of low catalytic activity.
Yano et al (chem. Commu.,1997,1129-1130) used MgO as a catalyst for propylene oxide and CO2The reaction for generating the propylene carbonate is carried out for 12 hours at 135 ℃, and the yield of the propylene carbonate is 41 percent.
Yamaguchi et Al (J.Am.chem.Soc.,1999,121,4526-2O3As catalyst for propylene oxide and CO2Reaction for generating propylene carbonate, and reaction for 24 hours at 100 ℃ to obtainThe yield to propylene carbonate was 88%, but the mass ratio of the catalyst to the substrate propylene oxide was as high as 2.2.
Tu et al (J.Catal.,2001,199,85-91) use Cs/KX as catalyst for ethylene oxide and CO2The reaction at 150 ℃ for 3 hours gave an ethylene carbonate yield of 14%.
Disclosure of Invention
The invention aims to solve the technical problem that the heterogeneous catalyst in the prior art has low activity, and provides a novel method for synthesizing ethylene carbonate. The method has the characteristic of high catalyst activity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for the synthesis of ethylene carbonate comprising the steps of contacting ethylene oxide and carbon dioxide under reaction conditions with a catalyst;
the catalyst comprises: at least one component AA selected from the amino acids lysine, arginine, histidine, alanine, glycine, glutamic acid, tryptophan or aspartic acid; and
at least one component HPA selected from phosphotungstic acid, silicotungstic acid, germanotungstic acid, arsenotungstic acid, phosphomolybdic acid, silicomolybdic acid, germanomolybdic acid or arsenomolybdic acid;
the weight ratio of AA to HPA is 1/40-1/4.
In the above technical solution, preferably, the component AA is selected from at least one of lysine, arginine, or histidine.
In the above technical solution, preferably, the component HPA is selected from at least one of phosphotungstic acid or silicotungstic acid.
In the technical scheme, the weight ratio of AA to HPA is preferably 1/20-1/8.
In the above technical scheme, the reaction conditions include: the reaction temperature is 60-200 ℃, and preferably 80-160 ℃; the reaction pressure is 0.1 to 10.0 MPa, preferably 0.5 to 8.0 MPa.
In the technical scheme, the weight ratio of the catalyst to the ethylene oxide is (0.001-1): 1, and preferably (0.005-0.5): 1.
The preparation method of the catalyst comprises the following steps: and respectively dissolving AA and HPA in dilute acid, slowly adding the dilute acid solution of HPA into the dilute acid solution of AA, stirring, and drying the obtained solid to obtain the catalyst. Wherein the diluted acid can be at least one diluted solution of nitric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, and preferably at least one of nitric acid and hydrochloric acid.
The method adopts the catalyst compounded by amino acid and heteropoly acid, the amino acid and heteropoly acid interact to generate the stable heterogeneous catalyst with acid-base double functions, and the amino acid component and heteropoly acid component have obvious synergistic catalytic action, thereby solving the problem of low activity of the heterogeneous catalyst. The catalyst of the invention has the reaction temperature of 130 ℃, the reaction pressure of 4.0MPa, and the mass ratio of the catalyst to the ethylene oxide of 0.05: the reaction lasts for 3 hours in 1 hour, the conversion rate of the ethylene oxide is 95.1 percent, the selectivity of the ethylene carbonate is 99.2 percent, the catalyst is reused for 5 times after being separated, the activity is reduced by less than 10 percent, and better technical effects are obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Weighing 0.92g of lysine (Lys) to be dissolved in 10.0ml of 0.5mol/L diluted hydrochloric acid solution to form a solution A, then dissolving 9.08g of phosphotungstic acid in 100.0ml of 0.5mol/L diluted hydrochloric acid solution to obtain a solution B, then dripping the solution B into the solution A at the speed of 3ml/min, stirring at room temperature for 9h, then heating to 60 ℃, continuing to stir for 2h, heating to 90 ℃, evaporating to dryness, and placing in a 120 ℃ oven overnight to obtain the catalyst AA/HPA-1, wherein the weight ratio of AA to HPA is 0.101.
[ example 2 ]
Weighing 1.95g of arginine (Arg) to be dissolved in 10.0ml of 0.5mol/L dilute hydrochloric acid solution to form a solution A, then dissolving 8.05g of phosphotungstic acid in 100.0ml of 0.5mol/L dilute hydrochloric acid solution to obtain a solution B, then dripping the solution B into the solution A at the speed of 3ml/min, stirring at room temperature for 2h, then heating to 60 ℃, continuing to stir for 10h, heating to 90 ℃, evaporating to dryness, and placing in a 120 ℃ oven overnight to obtain the catalyst AA/HPA-2, wherein the weight ratio of AA to HPA is 0.242.
[ example 3 ]
Weighing 0.26g of histidine (His) to be dissolved in 10.0ml of 0.5mol/L dilute hydrochloric acid solution to form a solution A, then dissolving 9.74g of silicotungstic acid in 100.0ml of 0.5mol/L dilute hydrochloric acid solution to obtain a solution B, then dripping the solution B into the solution A at the speed of 3ml/min, stirring for 5 hours at room temperature, then heating to 60 ℃, continuing to stir for 5 hours, heating to 90 ℃, evaporating to dryness, and placing in a 120 ℃ oven overnight to obtain a catalyst AA/HPA-3, wherein the weight ratio of AA to HPA is 0.026.
[ example 4 ]
The catalyst preparation procedure was the same as in example 1, except that 0.92g of tryptophan was used as the amino acid, 9.08g of phosphomolybdic acid was used as the heteropoly-acid, and the resulting catalyst was AA/HPA-4, and the weight ratio of AA to HPA in the catalyst was 0.101.
[ example 5 ]
The catalyst preparation procedure was the same as in example 1 except that 0.25g of Lys and 9.75g of phosphotungstic acid were used to give an AA/HPA-5 catalyst, the weight ratio of AA to HPA in the catalyst being 0.025.
[ example 6 ]
The catalyst preparation procedure was the same as in example 1, except that 1.69g of Lys and 9.31g of phosphotungstic acid were used, and the resulting catalyst was AA/HPA-6, the weight ratio of AA to HPA in the catalyst being 0.203.
[ example 7 ]
The catalyst AA/HPA-1 prepared in example 1 was used as a catalyst for the reaction of ethylene oxide and carbon dioxide to produce ethylene carbonate under the following reaction conditions: 150.0g of ethylene oxide and 7.5g of catalyst were charged in a 300ml autoclave and 1.0MPa of CO was charged2Heating to 130 deg.C, and charging CO2Maintaining the reaction pressure at 4.0MPa, cooling after 3h of reaction, opening the reaction kettle, analyzing the liquid by hue chromatography, and measuring the conversion rate (C) of the ethylene oxideEO% of the total amount of the components was 95.1% and ethylene carbonate (S)EC%) selectionThe sex was 99.2%.
[ examples 8 to 12 ]
The same conditions as described in [ example 7 ] were followed with the same change of the type of acid-base bifunctional catalyst used, and the results obtained are shown in table 1.
TABLE 1
| Examples | Catalyst and process for preparing same | Ethylene oxide conversion% | Ethylene carbonate selectivity,% |
| 8 | AA/HPA-2 | 79.2 | 98.6 |
| 9 | AA/HPA-3 | 71.6 | 99.0 |
| 10 | AA/HPA-4 | 85.6 | 98.5 |
| 11 | AA/HPA-5 | 70.3 | 99.0 |
| 12 | AA/HPA-6 | 84.5 | 99.1 |
Comparative example 1
Reaction of ethylene oxide with carbon dioxide Using the same method as in [ example 7 ] except that 0.92g of lysine was used as a catalyst, the conversion of ethylene oxide (C) was measuredEO%) was 31.5% and ethylene carbonate selectivity (S)EC%) was 96.3%.
Comparative example 2
Reaction of ethylene oxide with carbon dioxide Using the same method as in [ example 7 ] except that 9.08g of the catalyst was used, the conversion of ethylene oxide (C) was measuredEO%) was 21.3% and ethylene carbonate selectivity (S)EC%) was 49.3%.
[ examples 13 to 17 ]
AA/HPA-1 was used as a catalyst, and the reaction temperature, the reaction pressure, the mass ratio of the catalyst to ethylene oxide were varied, and the other conditions were the same as [ example 14 ], and the catalyst activity and selectivity were as shown in Table 2.
TABLE 2
| Examples | Reaction temperature of | Reaction pressure, MPa | catalyst/EO weight ratio | CEO％ | SEC％ |
| 13 | 62 | 9.5 | 1：1 | 38.9 | 94.3 |
| 14 | 160 | 0.5 | 0.002：1 | 43.5 | 95.8 |
| 15 | 80 | 5.0 | 0.02：1 | 34.2 | 99.1 |
| 16 | 150 | 6.0 | 0.2：1 | 96.5 | 98.1 |
| 17 | 140 | 2.0 | 0.005：1 | 88.8 | 98.1 |
[ example 18 ]
After the reaction was completed, the catalyst was separated and the reaction was carried out again under the same conditions as in example 7, and thus was repeatedly used five times, and it was found that the loss of the catalyst activity was less than 10%, as shown in table 3.
TABLE 3
| Number of times of application | CEO％ | SEC％ |
| 1 | 94.1 | 99.2 |
| 2 | 92.8 | 99.3 |
| 3 | 92.1 | 99.4 |
| 4 | 91.5 | 99.5 |
| 5 | 90.5 | 99.1 |
Claims (4)
1. A process for the synthesis of ethylene carbonate comprising the steps of contacting ethylene oxide and carbon dioxide under reaction conditions with a catalyst; the reaction conditions include: the temperature is 130-160 ℃, and the reaction pressure is 0.5-8.0 MPa; the weight ratio of the catalyst to the ethylene oxide is (0.005-0.5) to 1;
the catalyst comprises the following components: AA and HPA, wherein the AA is at least one of lysine, arginine, histidine, alanine, glycine, glutamic acid, tryptophan or aspartic acid; the HPA is at least one of phosphotungstic acid and phosphomolybdic acid;
the weight ratio of AA to HPA is 1/20-1/4;
the preparation method of the catalyst comprises the following steps: respectively dissolving AA and HPA in dilute acid, slowly adding the HPA solution into the dilute acid solution of AA, stirring, and drying the obtained solid to obtain the catalyst; wherein the dilute acid is at least one of nitric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid.
2. The method for synthesizing ethylene carbonate according to claim 1, wherein AA is at least one selected from lysine, arginine, and histidine.
3. The method for synthesizing ethylene carbonate according to claim 1, wherein the weight ratio of AA to HPA is 1/20-1/8.
4. The method for synthesizing ethylene carbonate according to claim 1, wherein the dilute acid is a dilute solution of at least one of nitric acid and hydrochloric acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3568225B2 (en) * | 1994-01-19 | 2004-09-22 | 三井化学株式会社 | Method for producing alkylene carbonate |
| CN102190648A (en) * | 2010-03-08 | 2011-09-21 | 中国科学院成都有机化学有限公司 | Method for synthesizing cyclic carbonate by using carbon dioxide and epoxide |
| CN102259011A (en) * | 2010-05-26 | 2011-11-30 | 拜耳材料科技(中国)有限公司 | Catalyst used for synthesizing cyclic carbonic ester, its preparation method and its purpose |
| WO2011153656A1 (en) * | 2010-06-07 | 2011-12-15 | 中国科学院过程工程研究所 | Process for preparing ethylene glycol catalyzed by ion liquid |
| CN103172608A (en) * | 2013-03-22 | 2013-06-26 | 中国科学院过程工程研究所 | Method for preparing cyclic carbonate through catalysis of amino acid composite catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602007008588D1 (en) * | 2006-09-15 | 2010-09-30 | Shell Int Research | PROCESS FOR THE PREPARATION OF ALKYLENE CARBONATE |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3568225B2 (en) * | 1994-01-19 | 2004-09-22 | 三井化学株式会社 | Method for producing alkylene carbonate |
| CN102190648A (en) * | 2010-03-08 | 2011-09-21 | 中国科学院成都有机化学有限公司 | Method for synthesizing cyclic carbonate by using carbon dioxide and epoxide |
| CN102259011A (en) * | 2010-05-26 | 2011-11-30 | 拜耳材料科技(中国)有限公司 | Catalyst used for synthesizing cyclic carbonic ester, its preparation method and its purpose |
| WO2011153656A1 (en) * | 2010-06-07 | 2011-12-15 | 中国科学院过程工程研究所 | Process for preparing ethylene glycol catalyzed by ion liquid |
| CN103172608A (en) * | 2013-03-22 | 2013-06-26 | 中国科学院过程工程研究所 | Method for preparing cyclic carbonate through catalysis of amino acid composite catalyst |
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